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Issue17 ozone

  1. 1. sis_17_RZ_.qxq:Layout 1 24.11.2010 9:40 Uhr Seite 46 Im ag e co ur te sy of NA AS A hole in the sky Twenty-five years ago, the discovery of the hole in the ozone layer hit the news. How have things developed since? Tim Harrison and Dudley Shallcross investigate. The Antarctic ozone hole at its annual maximum on 12 September 2008, stretching over 27 million square kilometres. This is considered a moderately large ozone hole, according to NASA Discovering the hole It was a serendipitous find, as Jonathan Shanklin, one of the hole’s discoverers, remembers: having joined the 35 British Antarctic Surveyw1 in 1977, he was supposed to digitise their backlog of ozone measurements – until then, 30 handwritten data sheets. As it turned out, this included the crucial decade, the 1970s, when ozone levels began to Altitude (kilometres) 25 Stratospheric Public domain image; image source: Wikimedia Commons drop. Ozone layer ozone There had already been growing concern that industrial 20 chlorofluorocarbons (CFCs) – organic compounds such as trichlorofluoromethane (CFCl3) and dichlorodifluo- romethane (CF2Cl2), then widely used as refrigerants, pro- 15 pellants (in spray cans) and solvents – might destroy the ozone layer. For an open day in 1983, Shanklin prepared a 10 Ozone Tropospheric graph – ironically to show that the ozone data from that increases ozone year were no different from 20 years before. Although this 5 from pollution was true for the overall ozone levels, he noticed that the springtime values did look lower from one year to the 0 next. Further studies corroborated this, and in 1985 Ozone concentration Shanklin and his colleagues Joe Farman and Brian Gardiner published their findings: each Southern Ozone is present throughout the lower atmosphere. Most Hemisphere spring, a hole gaped in the ozone layer above ozone is in the stratospheric ozone layer. Near Earth’s surface, the Antarctic, it was probably caused by CFCs, and it was the ozone levels increase as a result of pollution from human growing (Farman et al., 1985). activities 46 Science in School Issue 17 : Winter 2010
  2. 2. Science topics What is the chemistry behind this, and why is the ozone (hν) with a wavelength (l) around 200 nm and dissociateshole dangerous? into two oxygen atoms (O•) (reaction 1). Each of these can then combine with another oxygen molecule to formozone in the stratosphere ozone, if the pressure (M) is high enough (approximately Ozone (O3) is a much less stable triatomic form of oxy- one thousandth of an atmosphere) to stabilise the newlygen (O2). It is a pale blue gas present at low concentrations formed ozone molecule (reaction 2). The higher the alti-throughout the atmosphere – and a double-edged sword: tude, the faster the rate of reaction 1 (below 20 km alti-in the troposphere (see image on page 48), ozone is an air tude, no 200 nm photons occur because they have all beenpollutant which can damage the respiratory systems of absorbed in reaction 1). The rate of reaction 2, however, ishumans and other animals and burn sensitive plants. The faster closer to the ground, where atmospheric pressure isozone layer in the stratosphere, however, is beneficial, pre- higher. As a result, the maximum amount of ozone is cre-venting most of the harmful ultraviolet (UV) light emitted ated between about 25 and 30 km altitude (see graph onby the Sun from reaching Earth’s surface. page 46). The rate of ozone formation maximises in the strato- The stratosphere has two important consequences forsphere, the second highest layer of Earth’s atmosphere (at life on Earth. First, ozone itself absorbs high-energyabout 10-50 km altitude; see image), through a photo- UV radiation at around 250 nmchemical mechanism: (reaction 3):O2 + hν → O• + O• l ~ 200 nm (1) O3 + hν → O• + O2 l ~ 250 nm DH = - 90 kJ mol-1 (3)O• + O2 + M → O3 + M (2) Between them, oxygen (reaction 1) and ozone (reaction An oxygen molecule (O2) absorbs a photon of UV light 3) therefore filter out of the atmosphere most of the short- Chemistry Earth science catalytic cycles. Where do those organisms live? Ages 16+ Which chemical substances do they produce? · The chemical composition of the atmosphere and The ozone hole is a topical global issue, and you will its influence on the climate. Which gases is the find this article really helpful to get into the subject. atmosphere composed of? In which way do the The chemical processes involved are described in atmosphere’s properties determine climatic con- full detail. In chemistry lessons, the article can be ditions on Earth’s surface, and how does this dif- used to teach atomic structure and chemical bonds, fer on other planets? free radicals, catalytic cycles, and the influence of The article could also form the basis of a lesson on light and temperature on chemical reactions. how science is reported in the media. Students could compare this article to those in the general press: do For the earth science classroom, the article would fit they provide a balanced view of the question, men- in the context of the following topics: tioning both chemical and natural components lead- · Atmospheric influence on climate ing to the formation of the ozone hole? Do they min- · Biological processes occurring on Earth’s surface imise or overemphasise the phenomenon as a and affecting marine organisms whole? Why – due to journalists’ ignorance, political · Earth’s morphology and the distribution of moun- strategy or both? For further ideas on using news in tain ranges on Earth’s surface the science classroom, see Veneu-Lumb & Costa · The changing of the seasons, Earth’s axial tilt and (2010). rotation. Finally, the text is suitable as the basis of a compre- REViEW There is the opportunity for interdisciplinary work hension exercise, too. Possible questions are: linking chemistry and earth sciences. Possible topics include: · Why is this topic a much debated question nowadays? · The geographical distribution of the organisms · What is the role of natural factors in the growth that produce chemicals that are active in natural of the ozone hole? What about human factors? Teresa Celestino, Science in School Issue 17 : Winter 2010 47
  3. 3. sis_17_RZ_.qxq:Layout 1 24.11.2010 9:40 Uhr Seite 48 Image courtesy of Marlene Rau Layers of atmosphere leading to space 10 000 km Exosphere 690 km Public domain image; image source: Wikimedia Commons The four main reactions of oxygen in the ozone layer. Blue arrows indicate reac- tions, green dotted arrows indicate that a molecule from one reaction goes on to take part in another reaction. M denotes the pressure required for reaction 2 wave UV radiation between 200 and 300 nm, which would otherwise be very damaging to life on Earth. Second, reaction 3 produces a lot of heat, so the stratosphere is a warmer layer than the top of the troposphere (see image left), making the weather in the troposphere less extreme than it would otherwise be. Thermosphere Reactions 2 and 3 rapidly interconvert oxygen atoms and ozone. There is another slow reaction, though, which is known to destroy both oxygen atoms and ozone, namely the reaction between these two species: O• + O3 → O2 + O2 (4) Reactions 1-4 are summarised in the diagram above. 85 km Natural catalytic cycles reduce the levels of ozone Mesosphere In 1995, Paul Crutzen, Mario Molina and F Sherwood Rowland were awarded the Nobel Prize in Chemistry for their work on the formation and decomposi- tion of ozone in the stratosphere. What had they learned? In the 1970s, Crutzen and others discovered the existence of natural catalytic cycles that speed up 50 km reaction 4 and reduce the amount of ozone in the stratosphere (Crutzen, 1970, 1971): water (H2O), methane (CH4), nitrous oxide (N2O) and chloromethane (CH3Cl) are released into the atmosphere from biological processes occurring on Stratosphere Earth’s surface, and lead to the formation of radicals such as hydroxyl (OH•), nitric oxide (NO•) and chlorine (Cl•), which catalyse the decomposition of ozone. Reaction 5 shows how chloromethane releases chlorine radicals into the strat- osphere through photolysis, and reactions 6 and 7 are an example of a catalytic 6-20 km cycle (see diagram on page 49). The reactions of the other catalysts are analo- gous with reactions 6 and 7. Chloromethane is released in part by both marine Troposphere and terrestrial organisms, such as red macroalgae, white rot fungi and higher plants, to regulate chloride ion levels in the cells and – after 30 to 40 years – can reach the upper stratosphere (around 40 km altitude) where it is broken down 0 km by sunlight (photolysis): 48 Science in School Issue 17 : Winter 2010
  4. 4. sis_17_RZ_.qxq:Layout 1 24.11.2010 9:40 Uhr Seite 49 Science topics Image courtesy of Marlene Rau Chlorine radicals (for example from reaction 5) enter a catalytic cycle (reactions 6 and 7) of net ozone decomposition, which can be ter- minated by reac- tions 8 and 9. Blue arrows indicate reactions, green dotted arrows indi- cate that a mole- cule from one reac- tion goes on to take part in another reaction. M denotes the pressure required for reac- tion 9 CH3Cl + hν → •CH3 + Cl• λ~ 200 nm (5) predicted that CFCs would cause a significant additional The resulting chlorine free radical (Cl•) can then partici- loss of ozone at around 40 km altitude (see Molina & pate in a catalytic cycle: Rowland, 1974). However, when the ozone hole was final- ly found in 1985, it was in fact at around 20 km altitude, Cl• + O3 →ClO• + O2 (6) ClO• + O• →Cl• + O2 (7) over the South Pole in the Southern Hemisphere spring- time (see Farman et al., 1985). Reactions 6 and 7 taken together are in fact equivalent to It soon emerged that chlorine free radicals from the reaction 4, but happen much faster – in the case of the CFCs were responsible, but many questions remained chlorine / chlorine monoxide (ClO•) radical cycle, about unanswered. Why did the hole occur over the Pole? If it 30 000 times faster. So why do these catalytic cycles not occurred over the South Pole, why not also over the North destroy all the ozone? The answer lies in the termination Pole? Why only in spring? And why was the ozone hole at of these cycles via the formation of stable molecules: 20 km altitude instead of at 40 km, as predicted? After all, Cl• + CH4 →•CH3 + HCl (8) CFCs could not be broken down by sunlight at an altitude ClO• + •NO2 + M → ClONO2 + M (9) as low as 20 km, since the photon density was insufficient. Eventually, a chlorine free radical will encounter a For the same reason, not enough oxygen atoms are pro- methane molecule and react to form hydrochloric acid duced at this altitude for reaction 7 to occur. Many years (HCl, reaction 8). Similarly, a chlorine monoxide radical of further research revealed the complete story. will bind to a nitrogen dioxide radical, forming chlorine First, chlorine free radicals released from the CFCs, e.g. nitrate (ClONO2, reaction 9) – another pressure-dependent CFCl3 + hν→•CFCl2 + Cl• λ~ 200 nm (10) reaction that therefore works better at lower altitudes. Both hydrochloric acid and chlorine nitrate are very stable, could react with methane (reaction 8) forming hydrochlo- and the removal of chlorine and chlorine monoxide radi- ric acid, or with ozone (reaction 6) forming chlorine cals eventually stops the catalytic cycle. monoxide radicals, and through reaction 9 could subse- quently form chlorine nitrate. This sequence of reactions The Antarctic ozone hole puzzle would increase the concentrations of hydrocholoric acid It was not long before scientists realised that CFCs could and chlorine nitrate at around 40 km altitude globally. trigger a similar catalytic cycle of ozone degradation: in Each Southern Hemisphere winter, the South Pole is 1974, Molina and Rowland not only warned that levels of plunged into darkness for approximately three months. CFCs continued to increase without regulation, but also The air in the stratosphere above the South Pole cools Science in School Issue 17 : Winter 2010 49
  5. 5. sis_17_RZ_.qxq:Layout 1 24.11.2010 9:40 Uhr Seite 50 All year round over the Equator, in summer and autumn over the South Pole Early winter The formation and dissolution of the ozone hole over the year. 40 km (10) CFCl3 + hv (λ ~ 200 nm) → CFCl2 + Cl• Reactions 5 to 9 happen over (6) Cl• + O3 → ClO• + O2 (8) Cl• + CH4 → CH3• + HCl the Equator all year round, and (7) ClO• + O → Cl• + O2 (9) ClO• + NO2 → ClONO2 over the South Pole in summer and autumn. In early winter, the 30 km HCl and vortex forms over the South ClONO2 Pole, followed by the formation Vortex forms of polar stratospheric clouds in winter. In early spring, the sun- 20 km Cold and dark shine returns, but the vortex air sinks remains, and the reactions lead- ing to ozone removal over the South Pole take their course. In Equator late spring, the vortex breaks down, and ozone from mid-lati- tudes can mix in down; without UV radiation, reaction 3 does not occur, so HCl + ClONO2 →HNO3 + Cl2 polar stratospheric clouds (11) no heat is released. The air sinks and Earth’s rotation causes This reaction can take place all winter, if it is cold it to spin and form a vortex as it does so, like water going enough to form polar stratospheric clouds. When the sun- down a plughole. This vortex is so strong that no air from shine returns in spring, there are plenty of chlorine mole- outside can get in, and no air from inside can get out. Air cules at around 15-25 km altitude, which are photolysed to that is rich in hydrochloric acid and chlorine nitrate from 40 produce chlorine radicals: km altitude is drawn down into this cold and dark vortex. Cl2 + hν→ Cl• + Cl• λ~ 350 nm (12) In the extreme cold of the polar winter, the air in this vortex becomes so cold that below -78°C (195 K) and at an and subsequently chlorine monoxide radicals via reaction 6. altitude of 15-25 km, polar stratospheric clouds form from However, in the polar spring, reaction 7 (the formation water and / or acid ice crystals. of chlorine radicals and oxygen molecules from chlorine The first peculiar bit of chemistry is that hydrochloric monoxide radicals and oxygen radicals) is very slow, since acid and chlorine nitrate can adsorb onto polar stratos- there are so few oxygen atoms present due to the lack of pheric clouds and undergo a fast heterogeneous reaction 200 nm photons at this altitude, and here is where a sec- from gaseous to solid phase, producing nitric acid (HNO3) ond peculiar piece of chemistry occurs. At low tempera- that becomes incorporated into the ice crystals, whilst the tures, such as in the polar vortex – which is still very cold chlorine (Cl2) is released back into the gas phase. even in spring – chlorine monoxide radicals can form a 3% 15% HCI Image courtesy of Andrew Ryzhkov; image source: Wikimedia Commons CH3CI Natural Public domain image; image source: Wikimedia Commons 28% 3% HCFC-22 CFC-12 CFC-113 6% Anthropogenic CH3CCI3 10% CFC-11 CCI1 23% 12% Sources of stratospheric chlorine accord- ing to the WMO / UNEP Scientific Assessment of Ozone Depletion: 1998 Polar stratospheric clouds in Asker, Norway 50 Science in School Issue 17 : Winter 2010
  6. 6. sis_17_RZ_.qxq:Layout 1 24.11.2010 9:40 Uhr Seite 51 Science topics Image courtesy of Dudley Shallcross, Tim Harrison, Marlene Rau and Nicola Graf Winter Early spring Late spring HCl and Light returns, but vortex remains ClONO2 (12) Cl2 + hv (λ ~ 350 nm) → Cl• + Cl• Vortex breaks down and (6) Cl• + O3 → ClO•+ O2 ozone from mid-latitudes Polar stratospheric (13) ClO• + ClO• → ClOOCl can mix in clouds form (14) ClOOCl + hv (λ ~ 300 nm) → Cl•+Cl•+O2 (11) HCl + ClONO → HNO3 + Cl2 South Pole dimer, chlorine peroxide (ClOOCl): In late spring, the flow of ozone-rich air from above ClO• + ClO•→ ClOOCl (13) eventually warms the vortex via reaction 3, allowing the This dimer is unstable at room temperature but forms vortex to eventually break down. Since exchange with quite readily at low temperatures (below -30 °C) and can other parts of the atmosphere then becomes possible be photolysed: again, the ozone hole is filled with ozone from the sur- ClOOCl + hν→ Cl•+O2+Cl• λ~ 300 nm (14) rounding air. So even though reaction 7 cannot occur, reaction 14 In some years, the ozone hole over Antarctica has grown provides a way to regenerate chlorine free radicals with large enough to reach Australia, New Zealand, Chile and the help of light, and the catalytic cycle for ozone deple- Argentina, growing to 1.5 times the size of the USA; and tion can start in earnest now that the sunshine has when the ozone hole breaks up, the ozone-depleted air returned. drifts out into nearby (populated) areas, including South In what way does this differ from the natural catalytic Africa. For the people in these countries, the ozone hole cycles we looked at before – why is there a total removal poses a direct health threat. The main concern is the of ozone at some altitudes in this vortex? First, reaction 8 increased exposure to UV, which may cause skin cancer (which removes chlorine radicals and can terminate the and ocular cortical cataracts, as well as damage to the cycle) is very slow at the low temperatures found in the immune system. Furthermore, excessive UV radiation vortex, and therefore ineffective. Second, all the nitrogen damages plants and building materials. dioxide required for reaction 9 (which could likewise ter- minate the cycle, through the formation of ClONO2) has CFCs and ozone today been converted to nitric acid throughout the winter (e.g. Today, we have a good understanding of the physics through reactions 9 and 11) and it is not available to be and chemistry governing the ozone layer. Once the true regenerated since there is no upward flow in the vortex (at impact of CFCs on ozone depletion became apparent, gov- the base of the vortex, air flows from the South Pole to the ernments passed regulations to stop the use of CFCs, Equator, where the upward flow takes place). Therefore replacing them with alternative, shorter-lived, species the cycle carries on unchecked and destroys all the ozone (hydrofluorocarbons and hydrochlorofluorocarbons), at that level. Finally, without ozone, reaction 3, which which were to be phased out eventually too: the Montreal would otherwise warm this region, is absent, and so the Protocol of 1987 and especially its amendments in 1990 vortex lasts well into the spring, exacerbating the ozone and 1992, which speeded up the phase-out, were an envi- depletion. ronmental success. The only reason that the ozone hole is more severe over The most recent data from AGAGE (The Advanced the South Pole than the North Pole is that the spring tem- Global Atmospheric Gases Experiment)w2, which has been peratures in the stratosphere above the North Pole are monitoring levels of CFCs and their replacements since slightly warmer than those above the South Pole, because 1978, shows that even the atmospheric levels of dichlorod- there are more mountain ranges in the mid to high lati- ifluoromethane (CF2Cl2), the longest-lived CFC, are now tudes of the Northern Hemisphere, which change the decreasing: the legislation has been effective (see graph on dynamics of atmospheric flow, so there are fewer polar page 52). An ozone hole still forms each spring over the stratospheric clouds. South Pole, but estimates are that by 2050 this will no Science in School Issue 17 : Winter 2010 51
  7. 7. sis_17_RZ_.qxq:Layout 1 24.11.2010 9:40 Uhr Seite 52 Image courtesy of AGAGE longer happen, and that by 2080 the global ozone will return to 1950s levels. The atmospheric con- 550 centration of CFCs The ozone hole is the result of an CF2Cl2 mole fraction (ppt) increased rapidly and is 490 increased use of CFCs, which began now slowly decreasing in the 1930s – like any other gas, again. Data are given 430 CFCs take 30-40 years to reach the for CF2Cl2 , at the five upper stratosphere, which means that AGAGE surface meas- 370 there is a corresponding lag in their urement stations from effect on the ozone layer. We are cur- 1978 to the present day, 310 taken from the AGAGE rently experiencing the stratospheric websitew2 in September 250 chlorine peak resulting from the high- 2010 1980 1985 1990 1995 2000 2005 2010 est levels of CFC use in the 1980s – so the maximum size the ozone hole I Ireland I Oregon / California I Barbados I Samoa I Tasmania reaches each year should begin to decrease a few years from now. Although recovery is slow, we have Molina MJ, Rowland FS (1974) including CFCs and most non-CO2 definitely stopped a disaster: scien- Stratospheric sink for chlorofluo- greenhouse gases specified in the tists have calculated that if the use of romethanes – chlorine atomic- Kyoto protocol. To access their data CFCs had continued at its 1970s catalysed destruction of ozone. and for more information, see: growth rate of 3% per year, this Nature 249: 810-812. doi: would have led to a global ozone hole 10.1038/249810a0 Resources by 2060, with all the health problems The article is freely accessible on the that would bring (see image on page Nature website ( Sidney Chapman first derived the 53; Newman et al., 2009). or using the direct link: photolytic mechanism by which Perhaps the most important lesson ozone is formed and degraded. See: to be learned from the ozone hole is Newman PA et al. (2009) What would Chapman S (1930) On ozone and just how quickly our planet can have happened to the ozone layer if atomic oxygen in the upper change as a result of human impact – chlorofluorocarbons (CFCs) had not atmosphere. especially for the worse, but also for been regulated? Atmospheric Philosophical Magazine Series 7 the better – and that change is possi- Chemistry and Physics 9: 2113-2118. 10(64): 369-383. doi: ble if we take action concertedly, doi: 10.5194/acp-9-2113-2009 10.1080/14786443009461588 effectively and quickly. Patterson L (2010) A chemical bond: Jonathan Shanklin, one of the References Nick Barker, linking schools and scientists who discovered the universities in the UK. Science in ozone hole, published his reflec- Crutzen PJ (1970) Influence of nitro- School 15. tions 25 years after the discovery: gen oxides on atmospheric ozone /2010/issue15/nickbarker content. Quarterly Journal of the Shanklin J (2010) Reflections on the Veneu-Lumb F, Costa M (2010) Using ozone hole. Nature 465: 34-35. doi: Royal Meteorological Society 96: 320- news in the science classroom. 325. doi: 10.1002/qj.49709640815 10.1038/465034a. Science in School 15: 30-33. Crutzen PJ (1971) Ozone production Download the article free of charge rates in an oxygen-hydrogen-nitro- issue15/news from the Science in School website gen oxide atmosphere. Journal of ( Geophysical Research 76(30): 7311- Web references issue17/ozone), or subscribe to 7327. doi: 10.1029/JC076i030p07311 w1 – The British Antarctic Survey is Nature today: Farman JC, Gardner BG, Shanklin JD responsible for the UK’s national (1985) Large losses of total ozone in scientific activities in Antarctica. Nature has also published a collection Antarctica reveal seasonal See: of articles that have advanced our ClOx/NOx interaction. Nature 315: w2 – The Advanced Global understanding of the stratosphere 207-210. doi: 10.1038/315207a0 Atmospheric Gases Experiment, and the ozone layer, or told the The article is freely accessible on the AGAGE, is a NASA-sponsored ini- story of the discovery, some of Nature website ( tiative that has been measuring the which are freely available. See: or via the direct link: composition of the global atmos- phere continuously since 1978, ozonehole 52 Science in School Issue 17 : Winter 2010
  8. 8. sis_17_RZ_.qxq:Layout 1 24.11.2010 9:40 Uhr Seite 53 Science topics NASA images courtesy of the Goddard Space Flight Center Scientific Visualization Studio The Ozone Depletion website by scien- tist and author Rod Jenkins contains comprehensive information: The website of the United Nations Environment Programme’s OzonAction branch provides a 1974 1994 large collection of data and information about ozone and the Montreal Protocol. See: See also the pages of the United Nations Environment Programme Ozone secretariat, in English, French and Spanish: 2009 2020 NASA offers two online videos of atmospheric developments over the Arctic, as measured with the Upper Atmosphere Research Satellite (UARS). You can watch the increasing concentration of chlorine nitrate 2040 2060 in February / March 1993. See Ozone concentration (Dobson units) or use the direct link: 0 100 200 300 400 500 600 This video shows the formation of polar stratospheric clouds. See This is how the ozone layer would look if CFCs had not been banned or use the direct link: NASA’s Ozone Hole Watch page eruptions. See: or offers historical ozone maps, ozone use the direct link: In addition, NASA has published facts, an ozone-related multimedia images of a season in the life of the gallery, a collection of teaching Introduction to Atmospheric Chemistry ozone hole. See: modules about ozone-related by Harvard University’s Professor /vision/earth/lookingatearth/ topics, and more. See: Daniel J Jacob, which is freely 25TOMSAGU.html accessible as a PDF, contains a For the complete list of climate-related The University of Cambridge, UK, section on ozone, including the articles published in Science in School, diagram ‘Chronology of the ozone has compiled a virtual tour of the see: hole’ (chapter 10.3.3). See: ozone hole, its history and science. or The tour is available in English, use the direct link: French and German. See: Dudley Shallcross is a professor in or use Ozzy Ozone is a United Nations atmospheric chemistry and Tim the direct link: Harrison is a school teacher fellow at Environment Programme website the School of Chemistry, University of offering educational cartoons, The 74 scientists who attended the games, a glossary and more – Bristol, UK. For more information panel review meeting for the 2002 including downloadable education about the post of school teacher fellow, ozone assessment in Les Diablerets, packs with student and teacher see Patterson (2010). Switzerland, published 20 Questions handbooks for both primary and and Answers about the Ozone Layer, secondary school. All material is including the contributions of cycles available in English, French, and of solar activity and volcanic Spanish. See: Science in School Issue 17 : Winter 2010 53